The invention relates to novel pyrazolo[1,5-a]pyrimidines comprising at least one cationic group Z, Z being selected from quaternized aliphatic chains, aliphatic chains containing at least one quaternized saturated ring and aliphatic chains containing at least one quaternized unsaturated ring, to their use as oxidation base for the oxidation dyeing of keratinous fibres, to the dyeing compositions comprising them, and to the methods of oxidation dyeing which employ them.
It is known to dye keratinous fibres, and especially human hair, with dyeing compositions comprising oxidation dye precursors, especially ortho- or para-phenylenediamines, ortho- or para-aminophenols, and heterocyclic compounds such as diaminopyrazole derivatives, which are referred to generally as oxidation bases. The oxidation dye precursors or oxidation bases are colourless or slightly coloured compounds which, when combined with oxidizing products, have the capacity to give rise to coloured and colouring compounds by virtue of a process of oxidative condensation.
It is also known that the shades obtained with these oxidation bases may be varied by combining them with couplers or coloration modifiers, the latter being selected in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds.
The variety of molecules employed as oxidation bases and couplers makes it possible to obtain a rich palette of colours.
The so-called permanent coloration obtained by virtue of these oxidation dyes is required, moreover, to satisfy acertain number of requirements. Hence it must have no toxicological drawbacks, must allow shades of the desired intensity to be obtained, and must have good resistance to external agents (light, inclement weather, washing, permanent-waving, perspiration and friction).
The dyes must also allow white hair to be covered and, finally, they must be as unselective as possible; in other words, they must allow the smallest possible differences in coloration to be produced over the entire length of a single keratinous fibre, which may indeed be sensitized (i.e. damaged) differently between its tip and its root.
The applicant has now discovered, completely unexpectedly and surprisingly, that new pyrazolo[1,5-a]pyrimidines of formula (I) defined below, comprising at least one cationic group Z, Z being selected from quaternized aliphatic chains, aliphatic chains containing at least one quaternized saturated ring and aliphatic chains containing at least one quaternized unsaturated ring are not only suitable for use as oxidation dye precursors, but also make it possible to obtain dyeing compositions which lead to intense colorations in a wide palette of colours and have excellent properties of resistance to the various treatments which the keratinous fibres may undergo.
It is these discoveries which form the basis of the present invention.
The invention therefore provides, firstly, novel compounds of formula (I) below, and their addition salts with an acid: 
in which:
R1, R2 and R3, which may be identical or different, represent a hydrogen atom; a halogen atom; a group Z; a (C1-C6 alkyl)carbonyl radical; an amino(C1-C6 alkyl)carbonyl radical; an N-Z-amino(C1-C6 alkyl)carbonyl radical; an N-(C1-C6 alkyl)amino(C1-C6 alkyl)carbonyl radical; an N,N-di(C1-C6 alkyl)amino(C1-C6 alkyl)carbonyl radical; an amino(C1-C6 alkyl)carbonyl(C1-C6 alkyl) radical; an N-Z-amino(C1-C6 alkyl)carbonyl(C1-C6 alkyl) radical; an N-(C1-C6 alkyl)amino(C1-C6 alkyl)carbonyl(C1-C6 alkyl) radical; an N,N-di(C1-C6 alkyl)amino(C1-C6 alkyl)carbonyl(C1-C6 alkyl) radical; a carboxyl radical; a (C1-C6 alkyl)carboxyl radical; a (C1-C6 alkyl)sulphonyl radical; an aminosulphonyl radical; an N-Z-aminosulphonyl radical; an N-(C1-C6 alkyl)aminosulphonyl radical; an N,N-di(C1-C6 alkyl)-aminosulphonyl radical; an aminosulphonyl(C1-C6 alkyl) radical; an N-Z-aminosulphonyl(C1-C6 alkyl) radical; an N-(C1-C6 alkyl)aminosulphonyl(C1-C6 alkyl) radical; an N,N-di(C1-C6 alkyl)aminosulphonyl(C1-C6 alkyl) radical; a carbamyl radical; an N-(C1-C6 alkyl)carbamyl radical; an N,N-di(C1-C6 alkyl)carbamyl radical; a carbamyl(C1-C6 alkyl) radical; an N-(C1-C6 alkyl)carbamyl(C1-C6 alkyl) radical; an N,N-di(C1-C6 alkyl)carbamyl(C1-C6 alkyl) radical; a C1-C6 alkyl radical; a hydroxyl radical; a nitro radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a C1-C6 (C1-C6 alkoxy)alkyl radical; a C1-C6 trifluoroalkyl radical; a cyano radical; a group OR6 or SR6; an amino radical; an N-(C6-C6 alkyl)amino radical; an N,N-di(C1-C6 alkyl)amino radical (where the two alkyl substituents may form a 5- or 6-membered ring); an N-hydroxy(C1-C6 alkyl)amino radical; an N,N-bis(hydroxy(C1-C6 alkyl))amino radical; an N-polyhydroxy(C2-C6 alkyl)amino radical; an N,N-bis(polyhydroxy(C2-C6 alkyl))amino radical; an amino(C1-C6 alkyl)amino radical in which the terminal amino group is unsubstituted or substituted by one or two C1-C6 alkyl radicals, where the said alkyl radicals may form a saturated or unsaturated, 5- or 6-membered ring; an amino group protected by a (C1-C6 alkyl)carbonyl, trifluoro(C1-C6 alkyl)carbonyl, amino(C1-C6 alkyl)carbonyl, N-Z-amino(C1-C6 alkyl)-carbonyl, N-(C1-C6 alkyl)amino(C1-C6 alkyl)carbonyl, N,N-di(C1-C6 alkyl)amino(C1-C6 alkyl)carbonyl or formyl radical or by a group Z;
R6 denotes a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a group Z; a C1-C6 (C1-C6 alkoxy)alkyl radical; an aryl radical; a benzyl radical; a C1-C6 carboxyalkyl radical; a C1-C6 (C1-C6 alkyl)carboxyalkyl radical; a C1-C6 cyanoalkyl radical; a C1-C6 carbamylalkyl radical; a C1-C6 N-(C1-C6 alkyl)carbamylalkyl radical; a C1-C6 N,N-di(C1-C6 alkyl)carbamylalkyl radical; a C1-C6 trifluoroalkyl radical; a C1-C6 aminosulphonylalkyl radical; a C1-C6 N-Z-aminosulphonylalkyl radical; a C1-C6 N-(C1-C6 alkyl)aminosulphonylalkyl radical; a C1-C6 N,N-di(C1-C6 alkyl)aminosulphonylalkyl radical; a C1-C6 (C1-C6 alkyl)sulphinylalkyl radical; a C1-C6 (C1-C6 alkyl)sulphonylalkyl radical; a C1-C6 (C1-C6 alkyl)carbonylalkyl radical; a C1-C6 aminoalkyl radical; a C1-C6 aminoalkyl radical whose amine is substituted by one or two identical or different radicals selected from C1-C6 alkyl, monohydroxy(C1-C6 alkyl), polyhydroxy(C2-C6 alkyl), (C1-C6 alkyl)-carbonyl, formyl, trifluoro(C1-C6 alkyl)carbonyl and (C1-C6 alkyl)sulphonyl radicals or by a group Z;
A represents a group xe2x80x94NR4R5 or a hydroxyl radical;
R4 and R5, which are identical or different, represent a hydrogen atom; a group Z; a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; a C1-C6 (C1-C6 alkoxy)alkyl radical; an aryl radical; a benzyl radical; a C1-C6 cyanoalkyl radical; a C1-C6 carbamylalkyl radical; a C1-C6 N-(C1-C6 alkyl)carbamylalkyl radical; a C1-C6 N,N-di(C1-C6 alkyl)carbamylalkyl radical; a C1-C6 thiocarbamylalkyl radical; a C1-C6 trifluoroalkyl radical; a C1-C6 sulphoalkyl radical; a C1-C6 (C1-C6 alkyl)carboxyalkyl radical; a C1-C6 (C1-C6 alkyl)sulphinylalkyl radical; a C1-C6 aminosulphonylalkyl radical; a C1-C6 N-Z-aminosulphonylalkyl radical; a C1-C6 N-(C1-C6 alkyl)-aminosulphonylalkyl radical; a C1-C6 N,N-di(C1-C6 alkyl)aminosulphonylalkyl radical; a C1-C6 (C1-C6 alkyl)carbonylalkyl radical; a C1-C6 aminoalkyl radical; a C1-C6 aminoalkyl radical whose amine is substituted by one or two identical or different radicals selected from C1-C6 alkyl, C1-C6 monohydroxyalkyl, C2-C6 polyhydroxyalkyl, (C1-C6 alkyl)carbonyl, (C1-C6 alkyl)sulphonyl, formyl and trifluoro(C1-C6 alkyl)carbonyl radicals or by a group Z; one and only one of the radicals R4 and R5 may also represent a (C1-C6 alkyl)carbonyl; formyl; trifluoro(C1-C6 alkyl)carbonyl; amino(C1-C6 alkyl)carbonyl, N-Z-amino (C1-C6 alkyl)carbonyl; N-(C1-C6 alkyl)amino(C1-C6 alkyl)carbonyl; or N,N-di(C1-C6 alkyl)amino(C1-C6 alkyl)carbonyl radical;
Z is selected from the unsaturated cationic groups of formulae (II) and (III) below and the saturated cationic groups of formula (IV) below: 
in which:
D is a linker which represents an alkyl chain containing preferably 1 to 14 carbon atoms, is linear or branched and may be interrupted by one or more heteroatoms such as oxygen, sulphur or nitrogen atoms and may be substituted by one or more hydroxyl or C1-C6 alkoxy radicals, and may carry one or more ketone functions;
the ring members E, G, J, L and M, which are identical or different, represent a carbon, oxygen, sulphur or nitrogen atom;
n is an integer between 0 and 4, inclusively;
m is an integer between 0 and 5, inclusively;
the radicals R, which are identical or different, represent a group Z, a halogen atom, a hydroxyl radical, a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a nitro radical, a cyano radical, a C1-C6 cyanoalkyl radical, a C1-C6 alkoxy radical, a C1-C6 tri(C1-C6 alkyl)silanealkyl radical, an amido radical, an aldehydo radical, a carboxyl radical, a C1-C6 alkylcarbonyl radical, a thio radical, a C1-C6 thioalkyl radical, a (C1-C6 alkyl)thio radical, an amino radical, an amino radical protected by a (C1-C6 alkyl)carbonyl, carbamyl or (C1-C6 alkyl)sulphonyl radical; a group NHRxe2x80x3 or NRxe2x80x3Rxe2x80x2xe2x80x3 in which Rxe2x80x3 and Rxe2x80x2xe2x80x3, which are identical or different, represent a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical or a C2-C6 polyhydroxyalkyl radical;
R7 represents a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a C1-C6 cyanoalkyl radical, a C1-C6 tri(C1-C6 alkyl)silanealkyl radical, a C1-C6 (C1-C6 alkoxy)alkyl radical, a carbamyl(C1-C6 alkyl) radical, a C1-C6 (C1-C6 alkyl)carboxyalkyl radical, a benzyl radical, or a group Z;
R8, R9 and R10, which are identical or different, represent a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a C1-C6 (C1-C6 alkoxy)alkyl radical, a C1-C6 cyanoalkyl radical, an aryl radical, a benzyl radical, a C1-C6 amidoalkyl radical, a C1-C6 tri(C1-C6 alkyl)silanealkyl radical or a C1-C6 aminoalkyl radical whose amine is protected by a (C1-C6 alkyl)carbonyl, amido, carboxyl or (C1-C6 alkyl)sulphonyl radical; two of the radicals R8, R9 and R10 may also form, together with the nitrogen atom to which they are attached, a saturated 5- or 6-membered carbon-containing ring or one containing one or more heteroatoms such as, for example, a pyrrolidine ring, a piperidine ring, a piperazine ring or a morpholine ring, it being possible for the said ring to be unsubstituted or substituted by a halogen atom, a hydroxyl radical, a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a nitro radical, a cyano radical, a C1-C6 cyanoalkyl radical, a C1-C6 alkoxy radical, a C1-C6 tri(C1-C6 alkyl)silanealkyl radical, an amido radical, an aldehydo radical, a carboxyl radical, a C1-C6 ketoalkyl radical, a thio radical, a C1-C6 thioalkyl radical, a (C1-C6 alkyl)thio radical, an amino radical, or an amino radical protected by a (C1-C6 alkyl)carbonyl, carbamyl or (C1-C6 alkyl)sulphonyl radical; one of the radicals R8, R9 and R10 may also represent a second group Z, identical to or different from the first group Z;
R11 represents a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; an aryl radical; a benzyl radical; a C1-C6 aminoalkyl radical, a C1-C6 aminoalkyl radical whose amine is protected by a (C1-C6 alkyl)carbonyl, carbamyl or (C1-C6 alkyl)sulphonyl radical; a C1-C6 carboxyalkyl radical; a C1-C6 cyanoalkyl radical; a C1-C6 carbamylalkyl radical; a C1-C6 trifluoroalkyl radical; a C1-C6 tri(C1-C6 alkyl)silanealkyl radical; a C1-C6 sulphonamidoalkyl radical; a C1-C6 (C1-C6 alkyl)carboxyalkyl radical; a C1-C6 (C1-C6 alkyl)-sulphinylalkyl radical; a C1-C6 (C1-C6 alkyl) sulphonylalkyl radical; a C1-C6 (C1-C6 alkyl)ketoalkyl radical; a C1-C6 N-(C1-C6 alkyl)carbamylalkyl radical; a C1-C6 N-(C1-C6 alkyl) sulphonamidoalkyl radical;
a and y are integers equal to 0 or 1; with the following conditions:
in the unsaturated cationic groups of formula (II):
when a=0, the linker D is attached to the nitrogen atom,
when a=1, the linker D is attached to one of the ring members E, G, J or L,
y can adopt the value 1 only
1) when the ring members E, G, J and L simultaneously represent a carbon atom and when the radical R7 is carried by the nitrogen atom of the unsaturated ring; or else
2) when at least one of the ring members E, G, J and L represents a nitrogen atom to which the radical R7 is attached;
in the unsaturated cationic groups of formula (III):
when a=0, the linker D is attached to the nitrogen atom,
when a=1, the linker D is attached to one of the ring members E, G, J, L or M,
y can adopt the value 1 only when at least one of the ring members E, G, J, L and M represents a divalent atom and when the radical R7 is carried by the nitrogen atom of the unsaturated ring;
in the cationic groups of formula (IV):
when a=0, then the linker D is attached to the nitrogen atom which carries the radicals R8 to R10,
when a=1, then two of the radicals R8 to R10, together with the nitrogen atom to which they are attached, form a 5- or 6-membered saturated ring as defined above, and the linker D is carried by a carbon atom of the said saturated ring;
Xxe2x88x92 represents a monovalent or divalent anion and is selected preferably from a halogen atom such as chlorine, bromine, fluorine or iodine, a hydroxide, a hydrogen sulphate or a C1-C6 alkyl sulphate such as, for example, a methyl sulphate or an ethyl sulphate; with the proviso that the number of cationic groups Z is at least 1.
As indicated above, the colorations obtained with the oxidation dyeing composition in accordance with the invention are intense and make it possible to obtain a wide palette of colours. Moreover, they exhibit excellent properties of resistance with respect to the action of various external agents (light, inclement weather, washing, permanent-waving, perspiration, friction). These properties are particularly remarkable as regards notably, the resistance of the colorations obtained with respect to the action of light, washing, permanent-waving and perspiration.
In the formula (I) above, the alkyl and alkoxy radicals may be linear or branched.
Among the rings of the unsaturated groups Z of formula (II) above, mention may be made in particular, by way of example, of pyrrole, imidazole, pyrazole, oxazole, thiazole and triazole rings.
Among the rings of the unsaturated groups Z of formula (III) above, mention may be made in particular, by way of example, of pyridine, pyrimidine, pyrazine, oxazine and triazine rings.
Among the compounds of formula (I) above, mention may be made in particular of the following:
3-[3-(3-amino-5-methylpyrazolo[1,5-a]pyrimidin-7-ylamino)propyl]-1-(2-hydroxyethyl)-3H-imidazol-1-ium chloride,
3-[(3-aminopyrazolo[1,5-a]pyrimidin-7-ylcarbamoyl)-methyl)-1-methyl-3H-imidazol-1-ium chloride,
3-(3-amino-7-hydroxy-5-methylpyrazolo[1,5-a]-pyrimidin-6-ylmethyl)-1-methylpyridinium methyl sulphate,
3-(3-amino-7-hydroxy-5-methylpyrazolo[1,5-a]-pyrimidin-6-ylmethyl)-1-(2-hydroxyethyl)pyridinium chloride,
2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)methyl]-1,3-dimethyl-3H-imidazol-1-ium methyl sulphate,
3-[(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)-methyl]-1-methylpyridinium methyl sulphate,
3-[(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)-methyl]-1-methylpyridinium methyl sulphate,
2-(3,7-diamino-5-methylpyrazolo[1,5-a]pyrimidin-6-ylmethyl)-1,3-dimethyl-3H-imidazol-1-ium methyl sulphate,
2-(3-amino-7-hydroxy-5-methylpyrazolo[1,5-a]-pyrimidin-6-ylmethyl)-1,3-dimethyl-3H-imidazol-1-ium methyl sulphate,
2-(3,7-diaminopyrazolo[1,5-a]pyrimidin-2-yl)-1-methylpyridinium methyl sulphate,
[3-(3-amino-5-methylpyrazolo[1,5-a]pyrimidin-7-ylamino)propyl]trimethylammonium chloride,
[3-(3-amino-5-methylpyrazolo[1,5-a]pyrimidin-7-ylamino)propyl]trimethylammonium methyl sulphate,
1-[3-(3-amino-5-methylpyrazolo[1,5-a]pyrimidin-7-ylamino)propyl]-1-methylpiperidinium chloride,
1-[3-(3-amino-5-methylpyrazolo[1,5-a]pyrimidin-7-ylamino)propyl]-1-methylpiperidinium methyl sulphate,
4-[3-(3-amino-5-methylpyrazolo[1,5-a]pyrimidin-7-ylamino)propyl]-4-methylmorpholin-4-ium chloride,
4-[3-(3-amino-5-methylpyrazolo[1,5-a]pyrimidin-7-ylamino)propyl]-4-methylmorpholin-4-ium methyl sulphate, and their addition salts with an acid.
Among these compounds of formula (I), more particular preference is given to the following:
3-[3-(3-amino-5-methylpyrazolo[1,5-a]pyrimidin-7-ylamino)propyl]-1-(2-hydroxyethyl)-3H-imidazol-1-ium chloride,
3-(3-amino-7-hydroxy-5-methylpyrazolo[1,5-a]-pyrimidin-6-ylmethyl)-1-methylpyridinium methyl sulphate,
3-(3-amino-7-hydroxy-5-methylpyrazolo[1,5-a]-pyrimidin-6-ylmethyl)-1-(2-hydroxyethyl)pyridinium chloride,
3-(3-amino-7-hydroxy-5-methylpyrazolo[1,5-a]-pyrimidin-6-ylmethyl)-1-methylpyridinium chloride,
4-[3-(3-amino-5-methylpyrazolo[1,5-a]pyrimidin-7-ylamino)propyl]-4-methylmorpholin-4-ium chloride,
4-[3-(3-amino-5-methylpyrazolo[1,5-a]pyrimidin-7-ylamino)propyl]-4-methylmorpholin-4-ium methyl sulphate, and their addition salts with an acid.
The compounds of formula (I) in accordance with the invention may be readily obtained in accordance with well-known methods of the prior art:
firstly by reduction of the corresponding cationic nitroso or nitro compounds. In this case, reduction to the corresponding primary aromatic amine is carried out in accordance with conventional methods (J. Lehmman in Houben-Weyl, xe2x80x9cMethoden der Organischen Chemiexe2x80x9d, volume IV/1c: Reduction 1 page 491 to 537, 1980). The methods which are preferred in accordance with the invention involve metals such as Zn, Sn or Fe in an acidic medium such as aqueous hydrochloric acid or aqueous acetic acid in the presence or absence of a cosolvent such as methanol, ethanol or tetrahydrofuran. Catalytic hydrogenation is a preferred reduction method in accordance with the invention. This catalytic hydrogenation makes use of metals such as palladium, platinum or nickel. More particularly still, preference is given to palladium on carbon or to Raney nickel, or else to oxides such as PtO2 in solvents such as ethanol, ethanol, tetrahydrofuran or ethyl acetate in the presence or absence of an acid such as, for example, acetic acid. These catalytic reductions may also be carried out with formic acid in the presence of a trialkylamine such as triethylamine or with ammonium formate in the place of gaseous hydrogen. (S. Ram, R. E. Ehrenkaufer, Synthesis, 1988,91);
secondly, by reduction of the corresponding cationic azo compounds (reductive cleavage). Reduction to the corresponding primary aromatic amine is carried out in accordance with conventional methods (J. Lehmman in Houben-Weyl, xe2x80x9cMethoden der Organischen Chemiexe2x80x9d, volume IV/1c: Reduction 1 page 551 to 553, 1980; E. C. Taylor et al., J. Amer. Chem. Soc. 80, 421, 1958).
This step of reduction (to obtain a primary aromatic amine), which gives the synthesized compound its character as an oxidizable compound (oxidation base), and is followed or not by formation of a salt, is in general, for convenience, the last step of the synthesis.
This reduction may occur earlier on in the sequence of reactions leading to the preparation of the compounds of formula (I), and in accordance with well-known processes it is then necessary to xe2x80x9cprotectxe2x80x9d the primary amine created (for example by a step of acetylation, benzenesulphonation, etc.), to carry out subsequently the desired substitution(s) or modification(s) (including the quaternization), and to end with the xe2x80x9cdeprotectionxe2x80x9d (generally in an acidic medium) of the amine function.
When the synthesis is at an end, the compounds of formula (I) in accordance with the invention may, if appropriate, be recovered by well-known methods of the prior art, such as crystallization or distillation.
The invention additionally provides for the use of the compounds of formula (I) in accordance with the invention as oxidation base for the oxidation dyeing of keratinous fibres and, in particular, of human keratinous fibres such as the hair.
The invention also provides a composition for the oxidation dyeing of keratinous fibres and, in particular, of human keratinous fibres such as the hair, characterized in that it comprises as oxidation base, in a medium appropriate for dyeing, at least one compound of formula (I) in accordance with the invention.
The compound or compounds of formula (I) in accordance with the invention represent(s) preferably from 0.0005 to 12% by weight, approximately, of the total weight of the dyeing composition, and, more preferably still, from 0.005 to 6% by weight, approximately, of this weight.
The medium appropriate for dyeing (or vehicle) generally consists of water or a mixture of water and at least one organic solvent for solubilizing the compounds which would not be sufficiently soluble in water. By way of organic solvent, mention may be made, for example, of C1-C4 lower alkanols, such as ethanol and isopropanol; glycerol; glycols and glycol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl and monomethyl ether, and also aromatic alcohols such as benzyl alcohol or phenoxyethanol, similar products and mixtures thereof.
The solvents may be present in proportions of preferably between 1 and 40% by weight, approximately, relative to the total weight of the dyeing composition, and still more preferably between 5 and 30% by weight, approximately.
The pH of the dyeing composition according to the invention is generally between 3 and 12, approximately, and preferably between 5 and 11, approximately. It may be adjusted to the desired value by means of acidifying or basifying agents which are commonly employed in the dyeing of keratinous fibres.
Among the acidifying agents, mention may be made, by way of example, of mineral acids or organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic acid, and sulphonic acids.
Among the basifying agents, mention may be made, by way of example, of aqueous ammonia, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium hydroxide or potassium hydroxide, and the compounds of formula (V) below: 
in which W is a propylene residue optionally substituted by a hydroxyl group or a C1-C6 alkyl radical; and R12, R13, R14 and R15, which are identical or different, represent a hydrogen atom or a C1-C6 alkyl or C1-C6 hydroxyalkyl radical.
Furthermore, the dyeing composition according to the invention may comprise, in addition to the dyes defined above, at least one additional oxidation base, which may be selected from the oxidation bases conventionally used in oxidation dyeing and among which mention may be made in particular of para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols; ortho-aminophenols and heterocyclic bases other than the compounds of formula (I).
Among the para-phenylenediamines, mention may be made more particularly, by way of example, of para-phenylenediamine, para-tolylenediamine, 2,6-dimethyl-para-phenylenediamine, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-n-propyl-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(xcex2-hydroxypropyl)-para-phenylenediamine, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 4-amino-N-(xcex2-methoxyethyl)aniline, the para-phenylenediamines described in French Patent Application FR 2 630 438, and their addition salts with an acid.
Among the bisphenylalkylenediamines, mention may be made more particularly, by way of example, of N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)-1,3-diaminopropanol, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)ethylenediamine, N,Nxe2x80x2-bis(4-aminophenyl)-tetramethylenediamine, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(4-methylaminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(ethyl)-N,Nxe2x80x2-bis(4xe2x80x2-amino-3xe2x80x2-methylphenyl)-ethylenediamine, and their addition salts with an acid.
Among the para-aminophenols, mention may be made more particularly, by way of example, of para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(xcex2-hydroxyethylaminomethyl)phenol, and their addition salts with an acid.
Among the ortho-aminophenols, mention may be made more particularly, by way of example, of 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-ethylphenol, 5-acetamido-2-aminophenol, and their addition salts with an acid.
Among the heterocyclic bases, mention may be made more particularly, by way of example, of the pyridine derivatives, the non-cationic pyrimidine derivatives and the pyrazole derivatives.
Among the pyridine derivatives, mention may be made more particularly of the compounds described, for example, in Patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(xcex2-methoxyethyl)amino-3-amino-6-methoxypyridine, 3,4-diaminopyridine, and their addition salts with an acid.
Among the pyrimidine derivatives, mention may be made more particularly of the compounds described, roe for example, in German Patent DE 2 359 399 or Japanese Patents JP 88-169 571 and JP 91-10659 or Patent Application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and the pyrazolo-pyrimidine derivatives such as those mentioned in Patent Application FR-A-2 750 048 and among which mention may be made of pyrazolo[1,5-a]pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine; pyrazolo[1,5-a]pyrimidine-3,5-diamine; 2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine; 3-aminopyrazolo[1,5-a]pyrimidin-7-ol; 3-aminopyrazolo-[1,5-a]pyrimidin-5-ol; 2-(3-aminopyrazolo[1,5-a]-pyrimidin-7-ylamino)ethanol, 2-(7-aminopyrazolo[1,5-a]-pyrimidin-3-ylamino)ethanol, 2-((3-aminopyrazolo-[1,5-a]pyrimidin-7-yl)(2-hydroxyethyl)amino]ethanol, 2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)(2-hydroxyethyl)amino]ethanol, 5,6-dimethylpyrazolo-[1,5-a]pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo-[1,5-a]pyrimidine-3,7-diamine, 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo-[1,5-a]pyrimidine, their addition salts with an acid and their tautomeric forms, when a tautomeric equilibrium exists.
Among the pyrazole derivatives, mention may be made more particularly of the compounds described in Patents DE 3 843 892, DE 4 133 957 and Patent Applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4xe2x80x2-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(xcex2-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4xe2x80x2-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2xe2x80x2-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4-(xcex2-hydroxyethyl)amino-1-methylpyrazole, and their addition salts with an acid.
When they are used, these additional oxidation bases represent preferably from 0.0005 to 12% by weight, approximately, of the total weight of the dyeing composition, and more preferably still from 0.005 to 6% by weight, approximately, of this weight.
The oxidation dyeing compositions according to the invention may also include at least one coupler and/or at least one direct dye, in particular for the purpose of modifying the shades or enriching them with glints.
The couplers which may be used in the oxidation dyeing compositions according to the invention may be selected from the couplers used conventionally in oxidation dyeing, among which mention may be made in particular of meta-phenylenediamines, meta-aminophenols, meta-diphenols and the heterocyclic couplers such as, for example, the indole derivatives, indoline derivatives, pyridine derivatives and pyrazolones, and their addition salts with an acid.
These couplers are selected more particularly from 2-methyl-5-aminophenol, 5-N-(xcex2-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(xcex2-hydroxyethyloxy)benzene, 2-amino-4-(xcex2-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis (2,4-diaminophenoxy)propane, sesamol, xcex1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, and their addition salts with an acid.
When they are present, these couplers represent preferably from 0.0001 to 10% by weight, approximately, of the total weight of the dyeing composition, and more preferably still from 0.005 to 5% by weight, approximately, of this weight.
Generally speaking, the addition salts with an acid which may be used in the context of the invention (compounds of formula (I), additional oxidation bases and couplers) are selected in particular from the hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates.
The dyeing composition in accordance with the invention may also include various adjuvants which are conventionally employed in hair-dyeing compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, antioxidants, penetrants, sequestrants, perfumes, buffers, dispersants, conditioning agents such as, for example, silicones, film-formers, preservatives and opacifiers.
The person skilled in the art will of course take care to select this or these optional complementary compounds such that the advantageous properties intrinsically associated with the oxidation dyeing composition in accordance with the invention are not, or not substantially, adversely affected by the intended addition or additions.
The dyeing composition according to the invention may be presented in a variety of forms, such as in the form of liquids, creams, gels, or in any other form appropriate for carrying out dyeing of keratinous fibres and, in particular, of human hair.
The invention additionally provides a method of dyeing keratinous fibres and, in particular, human keratinous fibres such as the hair, employing the dyeing composition as defined above.
In accordance with this method, at least one dyeing composition as defined above is applied to the fibres, the colour being revealed at an acidic, neutral or alkaline pH with the aid of an oxidizing agent which is added to the dyeing composition right at the time of use or which is present in an oxidizing composition which is applied simultaneously or sequentially, separately.
In accordance with a preferred embodiment of the dyeing method of the invention, the dyeing composition described above is preferably mixed at the time of use with an oxidizing composition comprising, in a medium appropriate for dyeing, at least one oxidizing agent present in an amount sufficient to develop a coloration. The mixture obtained is then applied to the keratinous fibres and is left to act for from approximately 3 to 50 minutes, preferably for from 64 approximately 5 to 30 minutes, after which the fibres are rinsed, washed with shampoo, rinsed again and dried.
The oxidizing agent may be selected from the oxidizing agents which are conventionally used for the oxidation dyeing of keratinous fibres, among which mention may be made of hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, and enzymes such as peroxidases, laccases, tyrosinases and oxidoreductases, among which mention may be made in particular of the pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases and uricases.
The pH of the oxidizing composition comprising the oxidizing agent as defined above is such that, after mixing with the dyeing composition, the pH of the resultant composition that is applied to keratinous fibres varies preferably between approximately 3 and 12, and more preferably still between 5 and 11. It is adjusted to the desired value by means of acidifying or basifying agents which are commonly employed in dyeing keratinous fibres, such agents being as defined above.
The oxidizing composition as defined above may also include various adjuvants which are conventionally used in hair-dyeing compositions, such adjuvants being as defined above.
The composition which is ultimately applied to the keratinous fibres may be presented in various forms, such as in the form of liquids, creams or gels or in any other form appropriate for carrying out dyeing of keratinous fibres and, in particular, of human hair.
The invention also provides a multi-compartment dyeing device or xe2x80x9ckitxe2x80x9d, or any other packaging system having two or more compartments, of which a first compartment contains the dyeing composition as defined above and a second compartment contains the oxidizing composition as defined above. These devices may be equipped with a means allowing the desired mixture to be delivered to the hair, such as the devices described in Patent FR-2 586 913 in the name of the applicant.
The examples which follow are intended to illustrate the invention without limiting its scope.